UZM-26 Family of Crystalline Aluminosilicate Compositions and Method of Preparing the Compositions

ABSTRACT

This invention relates to a new family of crystalline aluminosilicate compositions designated the UZM-26 family. These include the species UZM-26P, UZM-26PX, UZM-26 and UZM-26X, which have unique structures. UZM-26P is an as synthesized layered composition, while UZM-26 is a calcined form of UZM-26P which has a three-dimensional structure. UZM-26PX is an ion-exchanged form of UZM-26P while UZM-26X is a calcined form of UZM-26PX which has a three-dimensional structure.

FIELD OF THE INVENTION

This invention relates to a new family of crystalline aluminosilicatecompositions designated the UZM-26 family. These include the speciesUZM-26P, UZM-26PX, UZM-26 and UZM-26X, which have unique structures.UZM-26P is an as synthesized layered composition, while UZM-26 is acalcined form of UZM-26P which has a three-dimensional structure.UZM-26PX is an ion-exchanged form of UZM-26P while UZM-26X is a calcinedform of UZM-26PX which has a three-dimensional structure.

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which aremicroporous and which are formed from corner sharing AlO₂ and SiO₂tetrahedra. Numerous zeolites, both naturally occurring andsynthetically prepared are used in various industrial processes.Synthetic zeolites are prepared via hydrothermal synthesis employingsuitable sources of Si, Al and structure directing agents such as alkalimetals, alkaline earth metals, amines, or organoammonium cations. Thestructure directing agents reside in the pores of the zeolite and arelargely responsible for the particular structure that is ultimatelyformed. These species balance the framework charge associated withaluminum and can also serve as space fillers. Zeolites are characterizedby having pore openings of uniform dimensions, having a significant ionexchange capacity, and being capable of reversibly desorbing an adsorbedphase which is dispersed throughout the internal voids of the crystalwithout significantly displacing any atoms which make up the permanentzeolite crystal structure. Zeolites can be used as catalysts forhydrocarbon conversion reactions, which can take place on outsidesurfaces as well as on internal surfaces within the pore.

Applicants have successfully prepared a new family of crystallinealuminosilicate compositions designated UZM-26. The family includes anas-synthesized layered composition designated UZM-26P; a calcined threedimensional microporous zeolitic composition designated UZM-26; anion-exchanged form of the as-synthesized composition designatedUZM-26PX; and a calcined three dimensional microporous zeoliticcomposition of the ion-exchanged composition, designated UZM-26X. Thetopologies of these UZM-26 family members are distinct from each otherand other aluminosilicate species in the prior art. The layeredcomposition can also be expanded and exfoliated by using cationicsurfactants. The as-synthesized layered composition, UZM-26P, isprepared using a structure directing agent such ashexyltrimethylammonium hydroxide, [CH₃(CH₂)₅NMe₃]⁺OH⁻, plus an alkaliearth metal such as Ca²⁺ using the Charge Density Mismatch Process forsynthesizing zeolites as described in US Patent Application PublicationNo. 2005/0095195.

SUMMARY OF THE INVENTION

As stated, the present invention relates to a new family of crystallinealuminosilicate compositions designated UZM-26. Accordingly, oneembodiment of the invention is a layered crystalline aluminosilicatedesignated UZM-26P having an empirical composition in the as synthesizedform and on an anhydrous basis expressed by an empirical formula of:

M_(m) ^(n+)R_(r) ^(p+)Al_(1-x)E_(x)Si_(y)O_(z)

where M is at least one exchangeable cation selected from the groupconsisting of alkali metal ions, alkaline earth metal ions, and rareearth metal ions, “m” is the mole ratio of M to (Al+E) and varies from0.05 to about 10.0, R is an organoammonium cation or an amine selectedfrom the group consisting of hexyltrimethylammonium (HTMA⁺),hexamethonium, pentyltrimethylammonium, choline, ethyltrimethylammonium(ETMA⁺), diethyldimethylammonium (DEDMA⁺), trimethylpropylammonium,trimethylbutylammonium, dimethyldiethanolammonium, tetraethylammonium(TEA⁺), tetrapropylammonium (TPA⁺), dimethylhexylamine, diethanolamineand mixtures thereof, “r” is the mole ratio of R to (Al+E) and has avalue of about 0.5 to about 10.0, “n” is the weighted average valence ofM and has a value of about 1 to about 3, “p” is the weighted averagevalence of R and has a value of about 1 to about 2, E is an elementselected from the group consisting of gallium, iron, boron and mixturesthereof, “x” is the mole fraction of E and has a value from 0 to about1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than5 to about 40 and “z” is the mole ratio of 0 to (Al+E) and has a valuedetermined by the equation:

z=(m·n+p·r+3+4·y)/2

and is characterized in that it has an x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table A:

TABLE A 2θ d (Å) I/Io % 5.32-5.88 16.60-15.02 m-vs 8.10-8.94 10.91-9.89 w-m 12.40-12.75 7.13-6.94 w-m 13.15-13.65 6.73-6.48 m 21.10-21.554.21-4.12 m 22.00-22.40 4.04-3.97 m 23.55-23.88 3.78-3.72 w-m24.95-25.31 3.57-3.52 m-vs 25.47-25.88 3.49-3.44 m 28.06-28.44 3.18-3.14w-m 49.78-50.28 1.83-1.81 m

Another embodiment of the invention is a process for preparing theUZM-26P composition described above. The process comprises forming areaction mixture containing reactive sources of M, R, Al, Si andoptionally E and heating the reaction mixture at a temperature of about60° C. to about 175° C. for a time sufficient to form thealuminosilicate, the reaction mixture having a composition expressed interms of mole ratios of the oxides of:

aM_(2/n)O:bR_(2/p)O:1-cAl₂O₃ :cE₂O₃ :dSiO₂ :eH₂O

where “a” has a value of about 0.05 to about 10.0, “b” has a value ofabout 2.5 to about 120, “c” has a value of 0 to about 1.0, “d” has avalue of about 10 to about 150, “e” has a value of about 25 to about6000.

Another embodiment of the invention is a crystalline microporous zeolitehaving a three-dimensional framework composed of at least tetrahedralSiO₂ units designated UZM-26. UZM-26 has an empirical composition on ananhydrous basis expressed by the empirical formula of:

M_(m) ^(n+)Al_(1-x)E_(x)Si_(y)O_(z)

where M is at least one exchangeable cation selected from the groupconsisting of alkali, alkaline earth, and rare earth metals, “m” is themole ratio of M to (Al+E) and varies from 0.05 to about 10.0, “n” is theweighted average valence of M and has a value of about 1 to about 3, Eis an element selected from the group consisting of gallium, iron, boronand mixtures thereof, “x” is the mole fraction of E and has a value from0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies fromgreater than 5 to about 40 and “z” is the mole ratio of O to (Al+E) andhas a value determined by the equation:

z=(m·n+3+4·y)/2

and is characterized in that it has an x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table B:

TABLE B 2θ d (Å) I/Io % 7.45-7.72 11.86-11.44 m-s 9.35-9.53 9.45-9.27m-s 12.30-13.00 7.19-6.80 m-s 13.25-13.73 6.68-6.44 m-s 15.20-15.805.82-5.60 w-m 21.06-21.62 4.22-4.11 m 22.16-22.62 4.01-3.93 m-vs23.73-24.06 3.75-3.70 m 25.15-25.44 3.54-3.50 vs 25.51-25.95 3.49-3.43m-vs 28.40-28.57 3.14-3.12 m 30.55-31.15 2.92-2.87 m 49.70-50.401.83-1.81 w-m

Another embodiment of the invention is a crystalline layered compositiondesignated UZM-26PX having an empirical composition on an anhydrousbasis expressed by an empirical formula of:

M′_(m) ^(n+)R_(r) ^(p+)Al_(1-x)E_(x)Si_(y)O_(z)

where M′ is at least one exchangeable cation selected from the groupconsisting of hydrogen ion, ammonium ion, alkali ion, alkaline earthion, transition metal ion and rare earth metal ion, “m” is the moleratio of M′ to (Al+E) and varies from 0.01 to about 10.0, R is anorganoammonium cation or an amine selected from the group consisting ofhexyltrimethylammonium (HTMA⁺), hexamethonium, pentyltrimethylammonium,choline, ethyltrimethylammonium (ETMA⁺), diethyldimethylammonium(DEDMA⁺), trimethylpropylaammonium, trimethylbutylammonium,dimethyldiethanolammonium, tetraethylammonium (TEA⁺),tetrapropylammonium (TPA⁺), dimethylhexylamine, diethanolamine andmixtures thereof, “r” is the mole ratio of R to (Al+E) and has a valueof about 0.01 to about 10.0, “n” is the weighted average valence of Mand has a value of about 1 to about 3, “p” is the weighted averagevalence of R and has a value of about 1 to about 2, E is an elementselected from the group consisting of gallium, iron, boron and mixturesthereof, “x” is the mole fraction of E and has a value from 0 to about1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than5 to about 40 and “z” is the mole ratio of 0 to (Al+E) and has a valuedetermined by the equation:

z=(m·n+p·r+3+4·y)/2

and is characterized in that it has the x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table C:

TABLE C 2θ d (Å) I/Io % 8.27-9.13 10.68-9.68  m 12.45-12.82 7.10-6.90 m13.33-13.61 6.64-6.50 m 22.21-22.48 4.00-3.95 m 23.74-24.05 3.74-3.70 m24.33-24.58 3.66-3.62 m 25.20-25.42 3.53-3.50 vs 28.22-28.75 3.16-3.10w-m 48.62-48.97 1.87-1.86 w-m 65.15-65.90 1.43-1.42 w

Another embodiment of the invention is a crystalline, microporousaluminosilicate zeolite formed by the calcination of UZM-26PX. UZM-26Xconsists of a three-dimensional framework composed of at leasttetrahedral SiO₂ units and an empirical composition on an anhydrousbasis expressed by the empirical formula of:

M1_(m) ^(n+)A_(1-x)E_(x)Si_(y)O_(z)

where M1 is at least one exchangeable cation selected from the groupconsisting of protons, alkali, alkaline earth, and rare earth metals,“m” is the mole ratio of M1 to (Al+E) and varies from 0.05 to about10.0, “n” is the weighted average valence of M1 and has a value of about1 to about 3, E is an element selected from the group consisting ofgallium, iron, boron and mixtures thereof, “x” is the mole fraction of Eand has a value from 0 to about 1.0, “y” is the mole ratio of Si to(Al+E) and varies from greater than 5 to about 40 and “z” is the moleratio of 0 to (Al+E) and has a value determined by the equation:

z=(m·n+3+4·y)/2

and is characterized in that it has an x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table D:

TABLE D 2θ d (Å) I/Io % 9.20-9.70 9.60-9.11 m 12.45-12.85 7.10-6.88 m-vs13.40-13.65 6.60-6.48 m-s 14.10-14.40 6.28-6.15 w-m 22.40-22.653.97-3.92 m-vs 23.85-24.10 3.73-3.69 w-m 25.22-25.45 3.53-3.50 vs25.89-26.10 3.44-3.41 m

These and other objects and embodiments of the invention will becomemore apparent after the detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared the a series of crystalline aluminosilicatecompositions designated the UZM-26 family of compositions which includethe as synthesized composition, UZM-26P, a calcined composition, UZM-26,an ion-exchanged composition, UZM-26PX, and an ion-exchanged versioncalcined composition, UZM-26X. Each of these species has a uniquetopology/structure. While UZM-26P and UZM-26PX are layered compositions,the calcined products, UZM-26 and UZM-26X are microporous threedimensional zeolites. UZM-26P has an empirical composition in theas-synthesized form and on an anhydrous basis expressed by the empiricalformula:

M_(m) ^(n+)R^(p+) _(r)Al_(1-x)E_(x)Si_(y)O_(z)

where M is at least one exchangeable cation and is selected from thegroup consisting of alkali metal ions, alkaline earth metal ions, andrare earth metal ions. Specific examples of the M cations include butare not limited to lithium, sodium, potassium, rubidium, cesium,calcium, strontium, barium, lanthanum, ytterbium and mixtures thereof,with calcium being preferred. R is an organoammonium cation or an amine,examples of which include but are not limited to thehexyltrimethylammonium cation, choline cation [(CH₃)₃NCH₂CH₂OH]⁺,ethyltrimethylammonium, diethyldimethylammonium,trimethylpropylammonium, trimethylbutylammonium,trimethylpentylammonium, dimethyldiethanolammonium, tetraethylammonium(TEA⁺), tetrapropylammonium TPA⁺, dimethylhexylamine, diethanolamine andmixtures thereof and “r” is the mole ratio of R to (Al+E) and variesfrom about 0.5 to about 10.0. Hexyltrimethylammonium is a preferredorganoammonium cation. The value of “p” which is the weighted averagevalence of R varies from 1 to about 2. The value of “n” which is theweighted average valence of M varies from about 1 to about 3 while “m”is the mole ratio of M to (Al+E) and varies from 0.05 to about 10. Theratio of silicon to (Al+E) is represented by “y” which varies from about5 to about 40. E is an element which is tetrahedrally coordinated, ispresent in the framework and is selected from the group consisting ofgallium, iron and boron. The mole fraction of E is represented by “x”and has a value from 0 to about 1.0, while “z” is the mole ratio of 0 to(Al+E) and is given by the equation:

z=(m·n+p·r+3+4·y)/2.

When M is only one metal, then the weighted average valence is thevalence of that one metal, i.e. +1 or +2.However, when more than one M metal is present, the total amount of:

M _(m) ^(n+) =M _(m1) ^((n1)+) +M _(m2) ^((n2)+) +M _(m3)^((n3)++ . . .)

and the weighted average valence “n” is given by the equation:

$n = \frac{{m_{1} \cdot n_{1}} + {m_{2} \cdot n_{2}} + {m_{3} \cdot n_{3}} + \ldots}{m_{1} + m_{2} + {m_{3}\mspace{11mu} \ldots}}$

When more than one organoammonium cation or amine is present, the totalamount of

R _(r) ^(p+) =R _(r1) ^((p1)+) +R _(r2) ^((p2)+) +R _(r3) ^((p3))+ . . .

And the weighted average valence “p” is given by the equation:

$p = \frac{{r_{1} \cdot p_{1}} + {r_{2} \cdot p_{2}} + {r_{3} \cdot p_{3}} + \ldots}{r_{1} + r_{2} + {r_{3}\mspace{11mu} \ldots}}$

UZM-26P, is prepared by a hydrothermal crystallization of a reactionmixture prepared by combining reactive sources of M, R, aluminum,silicon and optionally E. The sources of aluminum include but are notlimited to aluminum alkoxides, precipitated aluminas, aluminum metal,aluminum salts and alumina sols. Specific examples of aluminum alkoxidesinclude, but are not limited to aluminum ortho sec-butoxide and aluminumortho isopropoxide. Sources of silica include but are not limited totetraethylorthosilicate, colloidal silica, precipitated silica andalkali silicates. Sources of the E elements include but are not limitedto alkali borates, boric acid, precipitated gallium oxyhydroxide,gallium sulfate, ferric sulfate, and ferric chloride. Sources of the Mmetals include the halide salts, nitrate salts, acetate salts, andhydroxides of the respective alkali, alkaline earth, or rare earthmetals. R is an organoammonium cation or an amine selected from thegroup consisting of hexyltrimethylammonium, pentyltrimethylammonium,choline, ethyltrimethylammonium, diethyldimethylammonium, TEA, TPA,trimethylpropylammonium, trimethylbutylammonium,dimethyldiethanolammonium, dimethylhexylamine, diethanolamine andmixtures thereof, and the sources include the hydroxide, chloride,bromide, iodide and fluoride compounds. Specific examples includewithout limitation hexyltrimethylammonium hydroxide andhexyltrimethylammonium chloride, pentyltrimethylammonium hydroxide,ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide,tetraethylammonium hydroxide, tetrapropylammonium hydroxide,tetrapropylammonium chloride.

The reaction mixture containing reactive sources of the desiredcomponents can be described in terms of molar ratios of the oxides bythe formula:

aM_(2/n)O:bR_(2/p)O:1-cAl₂O₃ :cE₂O₃ :dSiO₂ :eH₂O

where “a” varies from about 0.05 to about 10.0, “b” varies from about2.5 to about 120, “c” varies from 0 to 1.0, “d” varies from about 10 toabout 150, and “e” varies from about 25 to about 6000. If alkoxides areused, it is preferred to include a distillation or evaporative step toremove the alcohol hydrolysis products. The reaction mixture is nowreacted at a temperature of about 60° C. to about 175° C. and preferablyfrom about 100° C. to about 150° C. for a period of about 1 day to about3 weeks and preferably for a time of about 6 days to about 15 days in asealed reaction vessel under autogenous pressure. After crystallizationis complete, the solid product is isolated from the reaction mixture bymeans such as filtration or centrifugation, and then washed withdeionized water and dried in air at ambient temperature up to about 100°C. A preferred synthetic approach to make UZM-26P utilizes the chargedensity mismatch process disclosed in US Patent Application PublicationNo. US 2005/0095195 which is incorporated by reference in its entirety.The charge density mismatch process allows multiple structure directingagents to cooperate to crystallize a single structure. The methodemploys appropriate quaternary ammonium hydroxides to solubilizealuminosilicate species, creating a reaction mixture which hasdifficulty crystallizing and condensing to form a solid under synthesisconditions. These preformed aluminosilicate species requirecrystallization-inducing agents such as alkali and alkaline earth metalsor more highly charged organoammonium cations that are separatelyintroduced and cooperate with the quaternary ammonium template to affectthe crystallization process. A preferred combination for the synthesisof UZM-26P is hexyltrimethylammonium hydroxide as the charge densitymismatch template and calcium as the crystallization inducing agent.

The UZM-26P crystalline layered aluminosilicate, which is obtained fromthe above-described process, is characterized by an x-ray diffractionpattern having at least the d-spacings and relative intensities setforth in Table A below.

TABLE A 2θ d (Å) I/Io % 5.32-5.88 16.60-15.02 m-vs 8.10-8.94 10.91-9.89 w-m 12.40-12.75 7.13-6.94 w-m 13.15-13.65 6.73-6.48 m 21.10-21.554.21-4.12 m 22.00-22.40 4.04-3.97 m 23.55-23.88 3.78-3.72 w-m24.95-25.31 3.57-3.52 m-vs 25.47-25.88 3.49-3.44 m 28.06-28.44 3.18-3.14w-m 49.78-50.28 1.83-1.81 m

UZM-26P is a layered composition and can be converted to a microporouscrystalline three-dimensional aluminosilicate zeolite, UZM-26, bycalcination. The condensation of the layers to form the microporousthree-dimensional UZM-26 occurs at calcination temperatures greater than400° C. and preferably at temperatures greater than 500° C. for timessufficient to decompose and remove the organoammonium template andeffect condensation. The time can vary considerably but is usually fromabout 3 hr to about 24 hr. The resulting UZM-26 is characterized by athree-dimensional framework composed of at least tetrahedral SiO₂ unitsand an empirical composition on an anhydrous basis expressed by theempirical formula of:

M_(m) ^(n+)Al_(1-x)E_(x)Si_(y)O_(z)

where M is at least one exchangeable cation selected from the groupconsisting of hydrogen ion, alkali, alkaline earth, and rare earthmetals, “m” is the mole ratio of M to (Al+E) and varies from 0.05 toabout 10.0, “n” is the weighted average valence of M and has a value ofabout 1 to about 3, E is an element selected from the group consistingof gallium, iron, boron and mixtures thereof, “x” is the mole fractionof E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to(Al+E) and varies from greater than 5 to about 40 and “z” is the moleratio of 0 to (Al+E) and has a value determined by the equation:

z=(m·n+3+4·y)/2

Where M is only one metal, then the weighted average valence is thevalence of that one metal, i.e. +1 or +2.However, when more than one M metal is present, the total amount of:

M _(m) ^(n+) =M _(m1) ^((n1)+) +M _(m2) ^((n2)+) +M _(m3) ^((n3)+)+ . ..

and the weighted average valence “n” is given by the equation:

$n = \frac{{m_{1} \cdot n_{1}} + {m_{2} \cdot n_{2}} + {m_{3} \cdot n_{3}} + \ldots}{m_{1} + m_{2} + {m_{3}\mspace{11mu} \ldots}}$

and is characterized in that it has the x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table B:

TABLE B 2θ d (Å) I/Io % 7.45-7.72 11.86-11.44 m-s 9.35-9.53 9.45-9.27m-s 12.30-13.00 7.19-6.80 m-s 13.25-13.73 6.68-6.44 m-s 15.20-15.805.82-5.60 w-m 21.06-21.62 4.22-4.11 m 22.16-22.62 4.01-3.93 m-vs23.73-24.06 3.75-3.70 m 25.15-25.44 3.54-3.50 vs 25.51-25.95 3.49-3.43m-vs 28.40-28.57 3.14-3.12 m 30.55-31.15 2.92-2.87 m 49.70-50.401.83-1.81 w-m

The UZM-26P aluminosilicate may also be ion-exchanged with hydrogen ion,ammonium ion, alkali, alkaline earth, transition metal, or rare earthmetal cations to form a new category of layered compositions with adistinct x-ray pattern designated UZM-26PX. The new structure resultsfrom a rearrangement of the layers with respect to each other as some orall of the organoammonium template and Ca are removed from UZM-26Pduring the ion-exchange process. UZM-26PX layers are composed of atleast tetrahedral SiO₂ units and an empirical composition on ananhydrous basis expressed by the empirical formula of:

M′_(m) ^(n+)R_(r) ^(p+)Al_(1-x)E_(x)Si_(y)O_(z)

where M is at least one exchangeable cation selected from the groupconsisting of hydrogen ion, ammonium ion, alkali metal ions, alkalineearth metal ions, transition metal ions and rare earth metal ions.Specific examples of the M cations include but are not limited tolithium, sodium, potassium, rubidium, cesium, calcium, strontium,barium, zinc, iron, copper, manganese, lanthanum, ytterbium and mixturesthereof. R is an organoammonium cation or an amine examples of which areselected from the group consisting of hexyltrimethylammonium (HTMA⁺),hexamethonium, pentyltrimethylammonium, choline, ethyltrimethylammonium(ETMA⁺), diethyldimethylammonium (DEDMA⁺), trimethylpropylammonium,trimethylbutylammonium, dimethyldiethanolammonium, tetraethylammonium(TEA⁺), tetrapropylammonium (TPA⁺), dimethylhexylamine, diethanolamineand mixtures thereof, “r” is the mole ratio of R to (Al+E) and has avalue of about 0.01 to about 10.0. The value of “m” is the mole ratio ofM to (Al+E) and varies from 0.01 to about 10.0, “n” is the weightedaverage valence of M and has a value of about 1 to about 3, “p” is theweighted average valence of R and has a value of about 1 to about 2, Eis an element selected from the group consisting of gallium, iron, boronand mixtures thereof, “x” is the mole fraction of E and has a value from0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies fromgreater than 5 to about 40 and “z” is the mole ratio of 0 to (Al+E) andhas a value determined by the equation:

z=(m·n+p·r+3+4·y)/2

When M′ is only one cation, then the weighted average valence is thevalence of that one cation, i.e. +1 or +2.However, when more than one M′ metal is present, the total amount of:

M′ _(m) ^(n+) =M′ _(m1) ^((n1)+) +M′ _(m2) ^((n2)+) +M′ _(m3) ^((n3)+)+. . .

and the weighted average valence “n” is given by the equation:

$n = \frac{{m_{1} \cdot n_{1}} + {m_{2} \cdot n_{2}} + {m_{3} \cdot n_{3}} + \ldots}{m_{1} + m_{2} + {m_{3}\mspace{11mu} \ldots}}$

And when more than one R′ organoammonium cation or amine is present, thetotal amount of:

R′ _(r) ^(p+) =R′ _(r1) ^((p1)+) +R′ _(r2) ^((p2)+) +R′ _(r3) ^((p3)+)+. . .

and the weighted average valence “p” is given by the equation:

$p = \frac{{r_{1} \cdot p_{1}} + {r_{2} \cdot p_{2}} + {r_{3} \cdot p_{3}} + \ldots}{r_{1} + r_{2} + {r_{3}\mspace{11mu} \ldots}}$

and is characterized in that it has an x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table C:

TABLE C 2θ d (Å) I/Io % 8.27-9.13 10.68-9.68  m 12.45-12.82 7.10-6.90 m13.33-13.61 6.64-6.50 m 22.21-22.48 4.00-3.95 m 23.74-24.05 3.74-3.70 m24.33-24.58 3.66-3.62 m 25.20-25.42 3.53-3.50 vs 28.22-28.75 3.16-3.10w-m 48.62-48.97 1.87-1.86 w-m 65.15-65.90 1.43-1.42 w

The ion-exchange of UZM-26P to form UZM-26PX is carried out by stirringUZM-26P suspended in a solution containing an excess of the exchangecation. The exchange is usually carried out for a period of 2-24 hoursat temperatures ranging from 15° C. to 95° C. The product is isolated byfiltration or centrifugation and is washed with deionized water. Thisprocess may be carried out as many times as necessary to achieve theexchange of cations.

Another embodiment of the UZM-26 family of crystalline aluminosilicatecompositions is derived from the ion-exchange of UZM-26P with anorganoammonium cation different from the starting organoammonium cation.As such, the layers may be “expanded” or exfoliated with appropriateorganoammonium salts such as cetyltrimethylammonium. These compositionsare highly variable with respect to an x-ray diffraction pattern, butseveral are included here in the examples. Such expanded compositionsmay also be further exchanged with pillaring agents, such as[Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺ or [Zr₄(OH)₈(H₂O)₁₆]⁸⁺ to make new microporouscompositions.

The exchanged aluminosilicate, UZM-26PX, is a layered composition andcan be converted to UZM-26X, a microporous aluminosilicate zeolite bycalcination. The condensation of the layers to form the microporousUZM-26X occurs at calcination temperatures greater than 400° C. andpreferably at temperatures greater than 500° C. for times sufficient todecompose and remove the organoammonium template and effectcondensation. Although the amount of time can vary considerably,typically the amount of time varies from about 2 hr to about 24 hr. Theresulting UZM-26X consists of a three-dimensional framework composed ofat least tetrahedral SiO₂ units and has an empirical composition on ananhydrous basis expressed by an empirical formula of:

M1_(m) ^(n+)Al_(1-x)E_(x)Si_(y)O_(z)

where M1 is at least one exchangeable cation selected from the groupconsisting of hydrogen ion, alkali metal ions, alkaline earth metalions, transition metal ions, and rare earth metal ions, “m” is the moleratio of M1 to (Al+E) and varies from 0.05 to about 10.0, “n” is theweighted average valence of M1 and has a value of about 1 to about 3, Eis an element selected from the group consisting of gallium, iron, boronand mixtures thereof, “x” is the mole fraction of E and has a value from0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies fromgreater than 5 to about 40 and “z” is the mole ratio of 0 to (Al+E) andhas a value determined by the equation:

z=(m·n+3+4·y)/2

When M1 is only one cation, then the weighted average valence is thevalence of that one cation, i.e. +1 or +2.However, when more than one M1 metal is present, the total amount of:

M1_(m) ^(n+) =M1_(m1) ^((n1)+) M1_(m2) ^((n2)+) +M1_(m3) ^((n3)+)+ . . .

and the weighted average valence “n” is given by the equation:

$n = \frac{{m_{1} \cdot n_{1}} + {m_{2} \cdot n_{2}} + {m_{3} \cdot n_{3}} + \ldots}{m_{1} + m_{2} + {m_{3}\mspace{11mu} \ldots}}$

and is characterized in that it has the x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table D:

TABLE D 2θ d (Å) I/Io % 9.20-9.70 9.60-9.11 m 12.45-12.85 7.10-6.88 m-vs13.40-13.65 6.60-6.48 m-s 14.10-14.40 6.28-6.15 w-m 22.40-22.653.97-3.92 m-vs 23.85-24.10 3.73-3.69 w-m 25.22-25.45 3.53-3.50 vs25.89-26.10 3.44-3.41 m

The microporous UZM-26 and UZM-26X compositions will contain some of theexchangeable or charge balancing cations in its pores. Theseexchangeable cations can be exchanged for other cations. The UZM-26 andUZM-26X zeolites may be modified in many ways to tailor them for use ina particular application. Modifications include calcination,ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof, as outlinedfor the case of UZM-4 in U.S. Pat. No. 6,776,975 B1 which isincorporated by reference in its entirety. Properties that can bemodified include porosity, adsorption, Si/Al ratio, acidity, thermalstability, etc.

The UZM-26 and UZM-26X compositions which are modified by one or moretechniques described in the '975 patent (herein UZM-26HS and UZM-26×HS)are described by the empirical formula on an anhydrous basis of:

M1′_(a) ^(n+)Al_((1-x))E_(x)Si_(y′)O_(z′)

where M1′ is at least one exchangeable cation selected from the groupconsisting of alkali, alkaline earth metals, transitions metals, rareearth metals, ammonium ion, hydrogen ion and mixtures thereof, “a” isthe mole ratio of M1′ to (Al+E) and varies from about 0.01 to about 50,“n” is the weighted average valence of M1′ and has a value of about +1to about +3, E is an element selected from the group consisting ofgallium, iron, boron, and mixtures thereof, “x” is the mole fraction ofE and varies from 0 to 1.0, y′ is the mole ratio of Si to (Al+E) andvaries from greater than 8 to virtually pure silica and z′ is the moleratio of 0 to (Al+E) and has a value determined by the equation:

z′=(a·n+3+4·y′)/2

By virtually pure silica is meant that virtually all the aluminum and/orthe E metals have been removed from the framework. It is well know thatit is virtually impossible to remove all the aluminum and/or E metal.Numerically, a zeolite is virtually pure silica when y′ has a value ofat least 3,000, preferably 10,000 and most preferably 20,000. Thus,ranges for y′ are from 8 to 3,000 preferably greater than 20 to about3,000; 8 to 10,000 preferably greater than 20 to about 10,000 and 8 to20,000 preferably greater than 20 to about 20,000.

In specifying the proportions of the zeolite starting composition oradsorption properties of the zeolite product and the like herein, the“anhydrous state” of the zeolite will be intended unless otherwisestated. The term “anhydrous state” is employed herein to refer to azeolite substantially devoid of both physically adsorbed and chemicallyadsorbed water.

The crystalline UZM-26 and UZM-26X zeolites of this invention can beused for separating mixtures of molecular species, removing contaminantsthrough ion exchange and catalyzing various hydrocarbon conversionprocesses. Separation of molecular species can be based either on themolecular size (kinetic diameter) or on the degree of polarity of themolecular species.

The UZM-26 and UZM-26X zeolites of this invention can also be used as acatalyst or catalyst support in various hydrocarbon conversionprocesses. Hydrocarbon conversion processes are well known in the artand include cracking, hydrocracking, alkylation of both aromatics andisoparaffin, isomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydration, dehydration,hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanationand syngas shift process. Specific reaction conditions and the types offeeds which can be used in these processes are set forth in U.S. Pat.No. 4,310,440 and U.S. Pat. No. 4,440,871 which are incorporated byreference. Preferred hydrocarbon conversion processes are those in whichhydrogen is a component such as hydrotreating or hydrofining,hydrogenation, hydrocracking, hydrodenitrogenation,hydrodesulfurization, etc.

Hydrocracking conditions typically include a temperature in the range of400° to 1200° F. (204-649° C.), preferably between 600° and 950° F.(316-510° C.). Reaction pressures are in the range of atmospheric toabout 3,500 psig (24,132 kPa g), preferably between 200 and 3000 psig(1379-20,685 kPa g). Contact times usually correspond to liquid hourlyspace velocities (LHSV) in the range of about 0.1 hr⁻¹ to 15 hr⁻¹,preferably between about 0.2 and 3 hr⁻¹. Hydrogen circulation rates arein the range of 1,000 to 50,000 standard cubic feet (scf) per barrel ofcharge (178-8,888 std. m³/m³), preferably between 2,000 and 30,000 scfper barrel of charge (355-5,333 std. m³/m³). Suitable hydrotreatingconditions are generally within the broad ranges of hydrocrackingconditions set out above.

The reaction zone effluent is normally removed from the catalyst bed,subjected to partial condensation and vapor-liquid separation and thenfractionated to recover the various components thereof. The hydrogen,and if desired some or all of the unconverted heavier materials, arerecycled to the reactor. Alternatively, a two-stage flow may be employedwith the unconverted material being passed into a second reactor.Catalysts of the subject invention may be used in just one stage of sucha process or may be used in both reactor stages.

Catalytic cracking processes are preferably carried out with the UZM-26and UZM-26X compositions using feedstocks such as gas oils, heavynaphthas, deasphalted crude oil residua, etc. with gasoline being theprincipal desired product. Temperature conditions of 850° to 1100° F.,LHSV values of 0.5 to 10 and pressure conditions of from about 0 to 50psig are suitable.

Alkylation of aromatics usually involves reacting an aromatic (C₂ toC₁₂), especially benzene, with a monoolefin to produce a linear alkylsubstituted aromatic. The process is carried out at an aromatic:olefin(e.g., benzene:olefin) ratio of between 5:1 and 30:1, a LHSV of about0.3 to about 6 hr⁻¹, a temperature of about 100° to about 250° C. andpressures of about 200 to about 1000 psig. Further details on apparatusmay be found in U.S. Pat. No. 4,870,222 which is incorporated byreference.

Alkylation of isoparaffins with olefins to produce alkylates suitable asmotor fuel components is carried out at temperatures of −30° to 40° C.,pressures from about atmospheric to about 6,894 kPa (1,000 psig) and aweight hourly space velocity (WHSV) of 0.1 to about 120. Details onparaffin alkylation may be found in U.S. Pat. No. 5,157,196 and U.S.Pat. No. 5,157,197, which are incorporated by reference.

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims.

The structures of the UZM-26 family of aluminosilicate compositions ofthis invention were determined by x-ray analysis. The x-ray patternspresented in the following examples were obtained using standard x-raypowder diffraction techniques. The radiation source was ahigh-intensity, x-ray tube operated at 45 kV and 35 ma. The diffractionpattern from the copper K-alpha radiation was obtained by appropriatecomputer based techniques. Flat compressed powder samples werecontinuously scanned at 2° to 70° (2θ). Interplanar spacings (d) inAngstrom units were obtained from the position of the diffraction peaksexpressed as θ where θ is the Bragg angle as observed from digitizeddata. Intensities were determined from the integrated area ofdiffraction peaks after subtracting background, “I_(o)” being theintensity of the strongest line or peak, and “I” being the intensity ofeach of the other peaks.

As will be understood by those skilled in the art the determination ofthe parameter 2θ is subject to both human and mechanical error, which incombination can impose an uncertainty of about ±0.4° on each reportedvalue of 2θ. This uncertainty is, of course, also manifested in thereported values of the d-spacings, which are calculated from the 2θvalues. This imprecision is general throughout the art and is notsufficient to preclude the differentiation of the present crystallinecompositions from each other and from the compositions of the prior art.In some of the x-ray patterns reported, the relative intensities of thed-spacings are indicated by the notations vs, s, m, and w whichrepresent very strong, strong, medium, and weak, respectively. In termsof 100×I/I_(o), the above designations are defined as:

-   -   w=0-15; m=15-60: s=60-80 and vs=80-100

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present. Finally,some peaks are identified with special identifiers as follows: verybroad (vbr); broad (br); and shoulder (sh).

In order to more fully illustrate the invention, the following examplesare set forth. It is to be understood that the examples are only by wayof illustration and are not intended as an undue limitation on the broadscope of the invention as set forth in the appended claims.

EXAMPLE 1 Hexyltrimethylammonium Hydroxide Solution

Hexyltrimethylammonium bromide, (99%) 1488.9 g, was dissolved in 2368.9g deionized water in a 5 liter 3-necked round bottom flask equipped withoverhead stirring. A 1 wt. % excess of Silver(I) oxide, (99%), 761.6 g,was added and stirred in the dark for 44 hours. The resultinghexyltrimethylammonium hydroxide solution was isolated by filtration.

Standardization of the hexyltrimethylammonium hydroxide solution viatitration with potassium acid phthalate to a phenolphthalein endpointrevealed the solution to be 30.03 wt. % hexyltrimethylammoniumhydroxide.

EXAMPLE 2 Hexyltrimethylammonium Aluminosilicate Solution

Hexyltrimethylammonium hydroxide, (30.03%), 455.04 g, was diluted with96.72 g deionized water while stirring. Aluminum tri sec-butoxide,(97%), 115.86 g, was added to the solution, which was then cooled in iceprior to the addition of tetraethylorthosilicate, (98%), 200.0 g withstirring. After hydrolysis was complete, the solution was transferred toa rotary evaporator to remove alcohol. A total of 163.7 g. of liquid wasremoved. Elemental analysis showed the solution to contain 3.74 wt. % Siand 1.77 wt. % Al.

EXAMPLE 3 Hexyltrimethylammonium Silicate Solution

Hexyltrimethylammonium hydroxide, (30.03%), 492.96 g, was diluted with1073.86 g deionized water and to it there were added 650.0 g oftetraethylorthosilicate, (98%) with stirring. After hydrolysis wascomplete, the solution was placed on a rotary evaporator to remove thealcohol. A total of 518.6 g of liquid was removed, after which 150 g ofdeionized water was added. Elemental analysis showed the solution tocontain 5.10 wt % Si.

EXAMPLE 4

A mixture was formed by adding 57.81 g of hexyltrimethylammoniumsilicate solution (Example 3), 10.02 g of hexyltrimethylammoniumaluminosilicate solution (Example 2), and 34.19 g ofhexyltrimethylammonium hydroxide (30.03%) to a beaker with stirring.This was followed by the dropwise addition of 11.56 g of a calciumacetate solution (Ca(OAc)₂.40H₂O), accompanied by vigorous stirring.Upon completion of the calcium acetate addition, the resulting mixturewas stirred for an additional hour and the reaction mixture was thendivided equally among four 45 ml Teflon®-lined autoclaves. The reactionmixtures were reacted at 150° C. for 10, 14, 17, and 21 daysrespectively.

The solid product from each autoclave was recovered by filtration,washed with de-ionized water and dried at 95° C. The products obtainedfrom all the reactions were identified to be UZM-26P by x-raydiffraction (XRD) analysis. Representative diffraction lines for theproduct isolated after 14 days are given below in Table 1. Elementalanalysis showed the product to consist of elements with the followingmole ratios: Si/Al=13.51, Ca/Al=1.81, N/Al=1.37, and C/N=5.90.

TABLE 1 2-Θ d(Å) I/I₀ % peaks 5.78 15.28 m 8.00 11.04 w sh 8.80 10.04 mvbr 12.66 6.99 m 13.50 6.55 m 17.87 4.96 w 21.46 4.14 m sh 22.30 3.98 m23.39 3.80 m 23.76 3.74 m 25.24 3.53 vs 25.76 3.46 m sh 26.99 3.30 w28.36 3.14 m 29.19 3.06 m 30.94 2.89 m 45.40 2.00 w 50.18 1.82 m

EXAMPLE 5

A mixture was formed by adding 60.77 g of hexyltrimethylammoniumsilicate solution (Example 3), 7.32 g of hexyltrimethylammoniumaluminosilicate solution (Example 2), and 34.93 g ofhexyltrimethylammonium hydroxide (30.03%) to a beaker with stirring. Tothe resulting mixture 10.56 g of calcium acetate solution(Ca(OAc)₂.40H₂O), were added dropwise with vigorous stirring. Uponcompletion of the calcium acetate addition, the resulting mixture wasstirred for an additional hour and then was divided equally among four45 ml Teflon®-lined autoclaves. The mixtures were reacted at 150° C. for10, 14, 17, and 21 days respectively.

The solid product from each autoclave was recovered by filtration,washed with de-ionized water and dried at 95° C. The products obtainedfrom all the reactions were identified to be UZM-26P by XRD analysis.Representative diffraction lines for the 10-day and the 21-day productare shown in Table 2 below. Elemental analysis showed the products toconsist of elements with the following mole ratios:

10-day product: Si/Al=15.46, Ca/Al=2.13, N/Al=1.96, and C/N=5.49;21-day product: Si/Al=16.67, Ca/Al=2.14, N/Al=1.84, and C/N=6.09.

TABLE 2 10-day product 21-day product 2-Θ d(Å) I/I₀ % peaks 2-Θ d(Å)I/I₀ % peaks 5.42 16.29 vs 5.44 16.23 vs 8.24 10.72 m vbr 7.82 11.30 wsh 12.48 7.09 m 8.30 10.65 m vbr 13.30 6.65 m 12.48 7.09 m 21.30 4.17 m13.28 6.66 m 22.24 3.99 m 21.22 4.18 m 23.06 3.85 m 22.14 4.01 m 23.643.76 m 22.82 3.89 m 25.06 3.55 s 23.64 3.76 m 25.79 3.45 m sh 25.02 3.56vs 28.14 3.17 m 25.60 3.48 m sh 28.48 3.13 w 28.18 3.16 m 28.94 3.08 m28.63 3.11 m 29.28 3.05 m 30.52 2.93 w 30.65 2.91 m 49.88 1.83 m 48.611.87 w 49.90 1.83 m 65.35 1.43 w

EXAMPLE 6

A mixture was formed by adding 65.03 g of hexyltrimethylammoniumsilicate solution (Example 3), 4.74 g of hexyltrimethylammoniumaluminosilicate solution (Example 2), and 33.06 g ofhexyltrimethylammonium hydroxide (30.03%) to a beaker with stirring. Tothe resulting mixture 10.93 g of calcium acetate solution(Ca(OAc)₂.40H₂O), were added dropwise with vigorous stirring. Uponcompletion of the calcium acetate addition, the resulting mixture wasstirred for an additional hour and then was divided equally among four45 ml Teflon®-lined autoclaves, which were reacted at 150° C. for 10,14, 17, and 21 days respectively.

The solid product from each autoclave was recovered by filtration,washed with de-ionized water and dried at 95° C. The products obtainedfrom all the reactions were identified to be UZM-26P by XRD analysis.Representative diffraction lines for the 14-day and the 21-day productare shown in Table 3 below. Elemental analysis showed the products toconsist of elements with the following mole ratios:

14-day product: Si/Al=21.25, Ca/Al=3.51, N/Al=2.46, and C/N=6.42;21-day product: Si/Al=23.14, Ca/Al=3.52, N/Al=2.42, and C/N=5.83.

TABLE 3 14-day product 21-day product 2-Θ d(Å) I/I₀ % peaks 2-Θ d(Å)I/I₀ % peaks 5.46 16.18 vs 5.44 16.23 vs 7.86 11.25 w sh 8.52 10.37 m br8.56 10.32 w br 12.52 7.07 m 12.50 7.08 w 13.24 6.68 m 13.32 6.64 m21.26 4.18 m 21.20 4.19 m 22.09 4.02 m 22.20 4.00 m 22.84 3.89 m 23.703.75 m 23.68 3.75 m 25.16 3.54 m 25.02 3.56 s 25.56 3.48 m sh 25.66 3.47m sh 28.24 3.16 w 28.16 3.17 m 28.56 3.12 m 29.19 3.06 w 29.02 3.07 m30.78 2.90 m 29.35 3.04 w 49.90 1.83 m 30.62 2.92 w 37.46 2.40 w 49.961.82 m

EXAMPLE 7

An aluminosilicate reaction mixture was prepared by first dissolving1.58 g of aluminum tri sec-butoxide (95+%) in 77.39 g ofhexyltrimethylammonium hydroxide, (30.03%), with vigorous stirring. Tothis mixture, colloidal silica (Ludox AS-40, 40% SiO₂), 23.90 g, wasadded. The reaction mixture was mixed for 1 hour at which point 14.06 gof a calcium acetate solution, (Ca(OAc)₂.40H₂O), was added dropwise. Theresultant reaction mixture was homogenized for an additional hour andthen divided equally between two 125 cc Teflon®-lined autoclaves andreacted at 150° C. for 14 days.

The solid product from each autoclave was recovered by filtration,washed with de-ionized water and dried at 95° C. The product obtainedfrom both autoclaves was identified to be UZM-26P by XRD analysis.Representative diffraction lines for the product from one of theautoclaves are shown in Table 4 below. Elemental analysis showed theproduct to consist of elements with the following mole ratios:Si/Al=16.79, Ca/Al=2.25, N/Al=1.42, and C/N=7.07.

TABLE 4 2-Θ d(Å) I/I₀ % peaks 5.52 16.00 vs 8.80 10.04 m br 12.54 7.05 m13.42 6.59 m 21.40 4.15 m 22.34 3.98 m 23.18 3.83 m 23.73 3.75 m 25.223.53 s 25.68 3.47 m sh 26.92 3.31 m 28.12 3.17 w 28.30 3.15 m 28.64 3.11m 29.01 3.08 w 30.51 2.93 m 48.72 1.87 w 50.16 1.82 m

EXAMPLE 8

This example details the synthesis of the UZM-26P composition which wasion-exchanged in the subsequent examples. An aluminosilicate reactionmixture was prepared by first dissolving 12.64 g of aluminumsec-butoxide (95⁺%) in 619.12 g of hexyltrimethylammonium hydroxide(30.03%) with vigorous stirring. This was followed by the addition ofcolloidal silica (Ludox AS-40, 40% SiO₂), 191.2 g, The resultingreaction mixture was homogenized for 1 hour Then there were added 112.48g of a calcium acetate solution (Ca(OAc)₂.40H₂O) dropwise with stirring.The reaction mixture was mixed for an additional hour and then loadedinto a 2 liter static autoclave and reacted for 13 days at 150° C.

The solid product was recovered by filtration, washed with de-ionizedwater and dried at 95° C. The resulting product was identified to beUZM-26P by XRD analysis. Representative diffraction lines for theproduct are shown in Table 5 below. Elemental analysis showed thecomposition of the product to consist of the following mole ratios:Si/Al=17.10, Ca/Al=2.45, N/Al=1.90, and C/N=6.86.

TABLE 5 2-Θ d(Å) I/I₀ % peaks 5.52 16.00 vs 8.52 10.37 m br 12.64 7.00 m13.48 6.57 m 14.06 6.29 w 21.28 4.17 m 22.26 3.99 m 23.80 3.74 w 24.413.64 m 25.18 3.53 s 25.58 3.48 m sh 25.96 3.43 m 28.34 3.15 m 49.98 1.82m 66.08 1.41 w

EXAMPLES 9-14

UZM-26 compositions are crystalline microporous zeolites derived fromthe calcination of the as-synthesized UZM-26P precursors. Examples 9-14present the synthesis of UZM-26 from UZM-26P at various conditions. Theresults from these examples are presented in Table 6 along with surfacearea analysis results. The calcination was carried out under a flow ofdry air, ramping first at 1° C./min to 350° C., holding for an hour,ramping at 1° C./min to the calcination temperature indicated in Table 6and holding at that temperature for the amount of time indicated. Aftercalcination, the materials were characterized by XRD analysis. Therepresentative diffraction lines for each UZM-26 composition are shownin Tables 7-10. The BET method was used to obtain the surface area data.

TABLE 6 Surface Area; Calcination Micropore Volume Diffraction ExampleParent UZM-26P Conditions (BET) Table 9 Example 4 525° C., dry air, 6 hr307 m2/g; 0.085 cc/g Table 7 10 Example 5, 10 day 540° C., dry air, 14hr 244 m2/g; 0.066 cc/g Table 8 11 Example 5, 21 day 525°, dry air, 6 hrnone Table 8 12 Example 6, 21 day 525° C., dry air, 4 hr 252 m2/g; 0.061cc/g Table 9 13 Example 7 525° C., dry air, 4 hr 269 m2/g; 0.067 cc/gTable 10 14 Example 8 525° C., dry air, 6 hr 209 m2/g; 0.057 cc/g Table10

TABLE 7 Example 9 2-Θ d(Å) I/I₀ % peaks 7.53 11.74 m 9.44 9.36 m br12.66 6.99 m 13.44 6.58 m 15.71 5.64 w br 21.28 4.17 m 22.30 3.98 m23.94 3.71 m 25.30 3.52 vs 25.70 3.46 m sh 28.51 3.13 m 30.82 2.90 m49.94 1.82 w

TABLE 8 Example 10 Example 11 2-Θ d(Å) I/I₀ % peaks 2-Θ d(Å) I/I₀ %peaks 7.66 11.53 m 7.52 11.75 m 9.44 9.36 m br 9.40 9.40 m br 12.58 7.03s 12.42 7.12 s 13.40 6.60 m 13.36 6.62 m 15.30 5.79 m 15.60 5.68 w br21.17 4.19 m 21.16 4.19 m 22.40 3.97 m br 22.26 3.99 s 23.90 3.72 m23.84 3.73 m 25.28 3.52 vs 25.24 3.53 vs 25.70 3.46 m sh 25.62 3.47 m sh28.54 3.13 m 28.32 3.15 m 30.77 2.90 m 30.82 2.90 m 49.82 1.83 m 49.951.82 m

TABLE 9 Example 12 2-Θ d(Å) I/I₀ % 7.57 11.68 s 9.48 9.32 m br 12.627.01 s 13.43 6.59 m 15.44 5.74 m br 21.30 4.17 m 22.49 3.95 m br 23.973.71 m 25.36 3.51 vs 25.80 3.45 m sh 28.48 3.13 m 30.76 2.90 m 49.941.82 m

TABLE 10 Example 13 Example 14 2-Θ d(Å) I/I₀ % peaks 2-Θ d(Å) I/I₀ %peaks 7.62 11.59 m 7.65 11.55 m 9.40 9.40 s br 9.40 9.40 m Br 12.60 7.02s 12.86 6.88 s 13.50 6.56 m 13.62 6.50 s 15.52 5.70 m 15.60 5.68 m 21.524.13 m 21.49 4.13 m 22.36 3.97 m 22.52 3.95 vs 23.96 3.71 m 23.82 3.73 m25.28 3.52 vs 25.30 3.52 vs 25.76 3.46 s sh 25.84 3.45 vs sh 28.58 3.12m 28.67 3.11 m 31.06 2.88 m 30.66 2.91 m 49.92 1.83 m 50.27 1.81 m

EXAMPLES 15-18

UZM-26PX compositions were obtained by ion-exchanging UZM-26Pcompositions. The UZM-26PX compositions are layered compositionsdistinct from the UZM-26P compositions, due to the removal of much ofthe Ca, or other initial metal cation and the organic template duringthe exchange process. The altered arrangement of aluminosilicate layersleads to a distinct x-ray diffraction pattern for these compositions.

EXAMPLE 15

The as-synthesized UZM-26P product from example 8 was exchanged withNH₄Cl by suspending 10 g of the UZM-26P powder in 500 g 0.5 M NH₄Clsolution at 75° C. for an hour with stirring. After an hour, theexchanged product was isolated by filtration and washed with deionizedwater. The process was repeated four times. The solid product was driedat 95° C. and identified to be UZM-26PX by XRD analysis. Representativediffraction lines for the product are shown in Table 11 below. Elementalanalysis showed the composition of the product to consist of thefollowing mole ratios: Si/Al=15.56, Ca/Al=0.03, N/Al=1.11, and C/N=4.43.

TABLE 11 2-Θ d(Å) I/I₀ % 8.46 10.45 m 12.56 7.04 m 13.46 6.57 m 22.383.97 m 23.84 3.73 m 24.43 3.64 m 25.32 3.51 vs 28.42 3.14 m 48.72 1.87 m65.31 1.43 w

EXAMPLE 16

The ammonium exchanged UZM-26PX material from Example 15 was nowexchanged with sodium as follows. Approximately 250 ml of 0.5 M NaClsolution was adjusted to pH 9 with 1 M NaOH solution, to which 2.4 g ofthe ammonium exchanged UZM-26PX material was added and stirred at roomtemperature for an hour. The product was isolated by filtration andwashed with de-ionized water. The process was repeated three times. Thesolid product was dried at 95° C. and identified to be UZM-26PX by XRDanalysis. Representative diffraction lines for the product are shown inTable 12 below. Elemental analysis showed the composition of the productto consist of the following mole ratios: Si/Al=17.68, Na/Al=0.24,N/Al=0.75, and C/N=5.96.

TABLE 12 2-Θ d(Å) I/I₀ % 8.92 9.91 m 12.64 7.00 m 13.48 6.56 m 22.353.98 m 23.84 3.73 m 24.44 3.64 m 25.28 3.52 vs 28.58 3.12 m 48.80 1.86 w65.45 1.42 w

EXAMPLE 17

The ammonium exchanged UZM-26PX material from Example 15 was exchangedwith calcium as follows. Approximately 250 ml of 0.5 M calcium acetatesolution was adjusted to pH 9 with 1 M NaOH solution, to which 2.4 g ofthe ammonium exchanged UZM-26PX material was added and stirred at roomtemperature for an hour. The product was isolated by filtration and waswashed with de-ionized water. The process was repeated three times. Thesolid product was dried at 95° C. and identified to be UZM-26PX by XRDanalysis. Representative diffraction lines for the product are shown inTable 13 below. Elemental analysis showed the composition of the productto consist of the following mole ratios: Si/Al=15.27, Ca/Al=0.30,N/Al=0.58, and C/N=7.66.

TABLE 13 2-Θ d(Å) I/I₀ % 8.96 9.86 m 12.72 6.96 m 13.54 6.53 m 22.403.97 m 23.98 3.71 m 24.52 3.63 m 25.38 3.51 vs 28.32 3.15 w 48.90 1.86 w65.46 1.42 w

EXAMPLE 18

The ammonium exchanged UZM-26PX material from Example 15 was exchangedwith lanthanum as follows. Approximately 250 ml of 0.5 M lanthanumacetate solution was adjusted to pH 7.5 with 1 M NaOH solution, to which2.4 g of the ammonium exchanged UZM-26PX material was added and stirredat room temperature for an hour. The product was isolated by filtrationand washed with de-ionized water. The process was repeated three times.The solid product was dried at 95° C. and was identified to be UZM-26PXby XRD analysis. Representative diffraction lines for the product areshown in Table 14 below. Elemental analysis showed the composition ofthe product to consist of the following mole ratios: Si/Al=15.55,La/Al=0.81, N/Al=0.75, and C/N=5.99.

TABLE 14 2-Θ d(Å) I/I₀ % 8.58 10.30 m 12.56 7.04 m 13.42 6.59 m 22.303.98 m 23.92 3.72 m 24.40 3.64 m 25.26 3.52 vs 28.66 3.11 m 48.70 1.87 w65.75 1.42 w

EXAMPLES 19 AND 20

The layers of UZM-26P or UZM-26PX can also undergo ion-exchange withsuitable organic materials vs. the metal, or ammonium ions describedabove. These compositions can be treated with organoammonium cations toaffect the exchange, or alternatively, the ammonium or proton form ofUZM-26PX may be treated with an amine to accomplish the exchange. Unlikethe metal cations used for exchange, the possible organoammonium andamine species that may be used for these exchanges may vary greatly insize. Often it is said that the layers are “expanded” uponion-exchanging with rather large organoammonium or amine species thatsignificantly increase the interlayer spacing. Because there are manypossible variations, it is difficult to characterize these materialswith a single powder x-ray diffraction pattern. These “expanded”compositions may be further treated by ion-exchange with the metalcations mentioned above or pillaring agents, such as[Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺, Zr₄(OH)₈(H₂O)₁₆]⁸⁺, etc., and calcined to makenew microporous compositions based on the UZM-26P-type layers.

EXAMPLE 19

As synthesized UZM-26P, 1 g, was suspended in a solution of 30 ml ofcetyltrimethylammonium chloride (25%) diluted with 70 ml of de-ionizedwater. The suspension was stirred for 24 hr, after which the product wasisolated by filtration, washed with de-ionized water, and dried at roomtemperature. Representative diffraction lines for the “expanded”exchange product are shown in Table 15 below.

TABLE 15 2-Θ d(Å) I/I₀ % 2.24 39.47 vs 4.52 19.56 m 6.82 12.95 w 8.5310.36 w 12.76 6.93 w 13.48 6.57 w 21.48 4.13 m 22.48 3.95 m 24.41 3.64 w25.26 3.52 m 26.47 3.37 w 50.19 1.82 m

EXAMPLE 20

As synthesized UZM-26P, 1 g, was suspended in a solution of 30 ml ofcetyltrimethylammonium chloride (25%) diluted with 70 ml of de-ionizedwater to which there were added 20 g tetrapropylammonium hydroxide,(40%). The suspension was heated to 95° C. and stirred for 16 hrs afterwhich the time the product was isolated by filtration, washed withde-ionized water, and dried at room temperature. Representativediffraction lines for the resulting “expanded” exchange product areshown in Table 16 below.

TABLE 16 2-Θ d(Å) I/I₀ % 2.20 40.21 vs 4.40 20.07 m 6.67 13.23 w 18.654.76 w 21.50 4.13 w 29.93 2.98 w 30.03 2.97 w 50.12 1.82 wExamples 19 and 20 are only representative of all the possible ways toexpand the layer spacing of the layered compositions of the invention.

EXAMPLES 21-24

As stated above, the UZM-26PX compositions, the layered, ion-exchangedversion of UZM-26P can be calcined to yield crystalline, microporouszeolites designated UZM-26X. These compositions have a distinct x-raypattern from those derived from the direct calcination of the UZM-26Pcompositions, which yield UZM-26. Examples 21-24 present the preparationof various UZM-26X compositions. The results of these experiments arepresented in Table 17 which provides data on which UZM-26PX sample wasused, the calcination conditions, the surface area data and identifieswhich table contains the respective x-ray diffraction data. Thecalcination is carried out under a flow of dry air or nitrogen, rampingfirst at 1° C./min to 350° C., holding for an hour, ramping at 1° C./minto the calcination temperature indicated in the Table 17 and holding atthat temperature for the amount of time indicated. After calcination,the compositions were characterized by XRD analysis. The representativediffraction lines for each UZM-26X composition are shown in Tables 18and 19. The BET method was used to obtain the surface area data.

TABLE 17 Surface Area; Parent UZM- Calcination Micropore VolumeDiffraction Example 26PX Conditions (BET) Table 21 Example 15 540° C.,dry air, 4 hr 379 m²/g; 0.078 cc/g Table 18 22 Example 16 550° C.,nitrogen, 6 hr 356 m²/g; 0.070 cc/g Table 18 23 Example 17 550° C.,nitrogen, 6 hr 332 m²/g; 0.066 cc/g Table 19 24 Example 18 550° C.,nitrogen, 6 hr 295 m²/g; 0.054 cc/g Table 19

TABLE 18 Example 21 Example 22 2-Θ d(Å) I/I₀ % peaks 2-Θ d(Å) I/I₀ %peaks 9.60 9.20 m br 9.51 9.30 m br 12.72 6.95 m 12.68 6.97 vs 13.546.54 m 13.56 6.53 s 14.21 6.23 m 14.30 6.19 m 22.56 3.94 m 22.50 3.95 s24.00 3.70 m 24.03 3.70 m 25.30 3.52 vs 25.38 3.51 vs 26.00 3.42 m sh25.98 3.43 s sh

TABLE 19 Example 23 Example 24 2-Θ d(Å) I/I₀ % peaks 2-Θ d(Å) I/I₀ %peaks 9.30 9.50 m br 9.61 9.20 m br 12.68 6.97 s 12.58 7.03 vs 13.526.54 s 13.51 6.55 s 14.22 6.23 w 14.32 6.18 m 22.48 3.95 s 22.49 3.95 s24.01 3.70 m 23.93 3.72 w 25.38 3.51 vs 25.38 3.51 vs 25.96 3.43 m sh26.05 3.42 s sh

1. A layered crystalline composition having an empirical composition inthe as-synthesized form and on an anhydrous basis expressed by anempirical formula of:M_(m) ^(n+)R_(r) ^(p+)Al_(1-x)E_(x)Si_(y)O_(z) where M is at least oneexchangeable cation selected from the group consisting of alkali metalions, alkaline earth metal ions, and rare earth metal ions, “m” is themole ratio of M to (Al+E) and varies from about 0.05 to about 10.0, R isan organoammonium cation or amine selected from the group ofhexyltrimethylammonium (HTMA⁺), hexamethonium, pentyltrimethylammonium,choline, ethyltrimethylammonium (ETMA⁺), diethyldimethyl ammonium(DEDMA⁺), trimethylpropylammonium, trimethylbutylammonium,dimethyldiethanolammonium, tetraethyl ammonium (TEA⁺),tetrapropylammonium (TPA⁺), dimethylhexylamine, diethanolamine, andmixtures thereof, “r” is the mole ratio of R to (Al+E) and has a valueof about 0.5 to about 10.0, “n” is the weighted average valence of M andhas a value of about 1 to about 3, “p” is the weighted average valenceof R and has a value of about 1 to about 2, E is an element selectedfrom the group consisting of gallium, iron, boron and mixtures thereof,“x” is the mole fraction of E and has a value from 0 to about 1.0, “y”is the mole ratio of Si to (Al+E) and varies from greater than 5 toabout 40 and “z” is the mole ratio of 0 to (Al+E) and has a valuedetermined by the equation:z=(m·n+p·r+3+4·y)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2θ d (Å) I/Io % 5.32-5.88 16.60-15.02 m-vs8.10-8.94 10.91-9.89  w-m 12.40-12.75 7.13-6.94 w-m 13.15-13.656.73-6.48 m 21.10-21.55 4.21-4.12 m 22.00-22.40 4.04-3.97 m 23.55-23.883.78-3.72 w-m 24.95-25.31 3.57-3.52 m-vs 25.47-25.88 3.49-3.44 m28.06-28.44 3.18-3.14 w-m 49.78-50.28 1.83-1.81 m


2. The composition of claim 1 where M is selected from the groupconsisting of lithium, sodium, potassium, rubidium, cesium, calcium,strontium, barium and mixtures thereof.
 3. The composition of claim 1where “x” is zero.
 4. The composition of claim 1 where R ishexyltrimethylammonium (HTMA⁺).
 5. The composition of claim 1 where R ischoline and M is calcium.
 6. A process for preparing a layeredcrystalline composition having an empirical composition in theas-synthesized form and on an anhydrous basis expressed by an empiricalformula of:M_(m) ^(n+)R_(r) ^(p+)Al_(1-x)E_(x)Si_(y)O_(z) where M is at least oneexchangeable cation selected from the group consisting of alkali metalions, alkaline earth metal ions, and rare earth metal ions, “m” is themole ratio of M to (Al+E) and varies from about 0.05 to about 10.0, R isan organoammonium cation or an amine selected from the group ofhexyltrimethylammonium (HTMA⁺), hexamethonium, pentyltrimethylammonium,choline, ethyltrimethylammonium (ETMA⁺), diethyldimethyl ammonium(DEDMA⁺), trimethylpropylammonium, trimethylbutylammonium,dimethyldiethanolammonium, tetraethyl ammonium (TEA⁺),tetrapropylammonium (TPA⁺), dimethylhexylamine, diethanolamine, andmixtures thereof, “r” is the mole ratio of R to (Al+E) and has a valueof about 0.5 to about 10.0, “n” is the weighted average valence of M andhas a value of about 1 to about 3, “p” is the weighted average valenceof R and has a value of about 1 to about 2, E is an element selectedfrom the group consisting of gallium, iron, boron and mixtures thereof,“x” is the mole fraction of E and has a value from 0 to about 1.0, “y”is the mole ratio of Si to (Al+E) and varies from greater than 5 toabout 40 and “z” is the mole ratio of 0 to (Al+E) and has a valuedetermined by the equation:z=(m·n+p·r+3+4·y)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2θ d (Å) I/Io % 5.32-5.88 16.60-15.02 m-vs8.10-8.94 10.91-9.89  w-m 12.40-12.75 7.13-6.94 w-m 13.15-13.656.73-6.48 m 21.10-21.55 4.21-4.12 m 22.00-22.40 4.04-3.97 m 23.55-23.883.78-3.72 w-m 24.95-25.31 3.57-3.52 m-vs 25.47-25.88 3.49-3.44 m28.06-28.44 3.18-3.14 w-m 49.78-50.28 1.83-1.81 m

the process comprising forming a reaction mixture containing reactivesources of M, R, Si and at least one of Al and E and heating thereaction mixture at a temperature of about 60° C. to about 175° C., fora time sufficient to form the composition, the reaction mixture having acomposition expressed in terms of mole ratios of the oxides of:aM_(2/n)O:bR_(2/p)O:1-cAl₂O₃ :cE₂O₃ :dSiO₂ :eH₂O where “a” has a valueof about 0.05 to about 10.0, “b” has a value of about 2.5 to about 120,“c” has a value of 0 to about 1.0, “d” has a value of about 10 to about150, “e” has a value of about 25 to about
 6000. 7. The process of claim6 where M is selected from the group consisting of lithium, cesium,sodium, potassium, rubidium, strontium, barium, calcium and mixturesthereof.
 8. The process of claim 6 where the source of M is selectedfrom the group consisting of halide salts, nitrate salts, acetate salts,hydroxides, sulfate salts and mixtures thereof.
 9. The process of claim6 where the source of E is selected from the group consisting of alkaliborates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate,ferric sulfate, ferric chloride and mixtures thereof.
 10. The process ofclaim 6 where the aluminum source is selected from the group consistingof aluminum isopropoxide, aluminum sec-butoxide, precipitated alumina,Al(OH)₃, aluminum metal and aluminum salts.
 11. The process of claim 6where the silicon source is selected from the group consisting oftetraethyorthosilicate, fumed silica, colloidal silica and precipitatedsilica.
 12. The process of claim 6 where the reaction mixture is reactedat a temperature of about 100° C. to about 150° C. for a time of about 6days to about 15 days.
 13. The process of claim 7 where R ishexyltrimethylammonium.
 14. The process of claim 7 where R ishexyltrimethylammonium and M is calcium.
 15. A crystalline microporouscomposition having a three-dimensional framework composed of at leasttetrahedral SiO₂ units and an empirical composition on an anhydrousbasis expressed by the empirical formula of:M_(m) ^(n+)Al_(1-x)E_(x)Si_(y)O_(z) where M is at least one exchangeablecation selected from the group consisting of hydrogen ion, alkali,alkaline earth, and rare earth metals, “m” is the mole ratio of M to(Al+E) and varies from 0.05 to about 10.0, “n” is the weighted averagevalence of M and has a value of about 1 to about 3, E is an elementselected from the group consisting of gallium, iron, boron and mixturesthereof, “x” is the mole fraction of E and has a value from 0 to about1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than5 to about 40 and “z” is the mole ratio of 0 to (Al+E) and has a valuedetermined by the equation:z=(m·n+3+4·y)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table B: TABLE B 2θ d (Å) I/Io % 7.45-7.72 11.86-11.44 m-s9.35-9.53 9.45-9.27 m-s 12.30-13.00 7.19-6.80 m-s 13.25-13.73 6.68-6.44m-s 15.20-15.80 5.82-5.60 w-m 21.06-21.62 4.22-4.11 m 22.16-22.624.01-3.93 m-vs 23.73-24.06 3.75-3.70 m 25.15-25.44 3.54-3.50 vs25.51-25.95 3.49-3.43 m-vs 28.40-28.57 3.14-3.12 m 30.55-31.15 2.92-2.87m 49.70-50.40 1.83-1.81 w-m


16. The composition of claim 15 where M is selected from the groupconsisting of Li, Na, K, Cs, Ca, Ba, Sr, La and Yb.
 17. A crystallinelayered composition having an empirical composition on an anhydrousbasis expressed by an empirical formula of:M′ _(m) ^(n+)R_(r) ^(p+)Al_(1-x)E_(x)Si_(y)O_(z) where M′ is at leastone exchangeable cation selected from the group consisting of hydrogenion, ammonium ion, alkali ion, alkaline earth ion, transition metal ionand rare earth metal ion, “m” is the mole ratio of M′ to (Al+E) andvaries from 0.01 to about 10.0, R is an organoammonium cation or anamine selected from the group consisting of hexyltrimethylammonium(HTMA⁺), hexamethonium, pentyltrimethylammonium, choline,ethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺),trimethylpropylammonium, trimethylbutylammonium,dimethyldiethanolammonium, tetraethylammonium (TEA⁺),tetrapropylammonium (TPA⁺), dimethylhexylamine, diethanolamine andmixtures thereof, “r” is the mole ratio of R to (Al+E) and has a valueof about 0.01 to about 10.0, “n” is the weighted average valence of Mand has a value of about 1 to about 3, “p” is the weighted averagevalence of R and has a value of about 1 to about 2, E is an elementselected from the group consisting of gallium, iron, boron and mixturesthereof, “x” is the mole fraction of E and has a value from 0 to about1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than5 to about 40 and “z” is the mole ratio of O to (Al+E) and has a valuedetermined by the equation:z=(m·n+p·r+3+4·y)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table C: TABLE C 2θ d (Å) I/Io % 8.27-9.13 10.68-9.68  m12.45-12.82 7.10-6.90 m 13.33-13.61 6.64-6.50 m 22.21-22.48 4.00-3.95 m23.74-24.05 3.74-3.70 m 24.33-24.58 3.66-3.62 m 25.20-25.42 3.53-3.50 vs28.22-28.75 3.16-3.10 w-m 48.62-48.97 1.87-1.86 w-m 65.15-65.901.43-1.42 w


18. The composition of claim 17 where M′ is H⁺, NH₄ ⁺, Li, Na, Ca, Sr,La, Yb, Fe, Co, Cu, Zn, and Mn.
 19. The composition of claim 17 where Ris hexyltrimethylammonium, hexamethonium, choline,ethyltrimethylammonium, and dimethylhexylamine.
 20. A crystallinemicroporous zeolitic composition having a three-dimensional frameworkcomposed of at least tetrahedral SiO₂ units and an empirical compositionon an anhydrous basis expressed by the empirical formula of:M1_(m) ^(n+)Al_(1-x)E_(x)Si_(y)O_(z) where M1 is at least oneexchangeable cation selected from the group consisting of protons,alkali, alkaline earth, transition metals, and rare earth metals, “m” isthe mole ratio of M1 to (Al+E) and varies from 0.05 to about 10.0, “n”is the weighted average valence of M1 and has a value of about 1 toabout 3, E is an element selected from the group consisting of gallium,iron, boron and mixtures thereof, “x” is the mole fraction of E and hasa value from 0 to about 1.0, “y” is the mole ratio of Si to (Al+E) andvaries from greater than 5 to about 40 and “z” is the mole ratio of O to(Al+E) and has a value determined by the equation:z=(m·n+3+4·y)/2 and is characterized in that it has an x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable D: TABLE D 2θ d (Å) I/Io % 9.20-9.70 9.60-9.11 m 12.45-12.857.10-6.88 m-vs 13.40-13.65 6.60-6.48 m-s 14.10-14.40 6.28-6.15 w-m22.40-22.65 3.97-3.92 m-vs 23.85-24.10 3.73-3.69 w-m 25.22-25.453.53-3.50 vs 25.89-26.10 3.44-3.41 m


21. The composition of claim 20 where M1 is H⁺, NH₄ ⁺, Li, Na, Ca, Sr,La, Yb, Fe, Co, Cu, Zn, and Mn.